CN1267301A - Methoximinomethyloxadiazines used as pesticides - Google Patents
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- CN1267301A CN1267301A CN98808157A CN98808157A CN1267301A CN 1267301 A CN1267301 A CN 1267301A CN 98808157 A CN98808157 A CN 98808157A CN 98808157 A CN98808157 A CN 98808157A CN 1267301 A CN1267301 A CN 1267301A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Furan Compounds (AREA)
Abstract
The invention relates to new methoximinomethyloxadiazines, two methods for their production, and their use as pesticides. The invention also relates to new intermediary products and a method for their production.
Description
The invention relates to a novel methoximinomethyl oxadiazine compound, two preparation methods thereof and application thereof as pesticide. The invention also relates to novel intermediates and processes for their preparation.
Certain methoxyiminomethyl oxadiazines are known to have fungicidal activity (WO 96-25406). However, the activity of these prior art compounds, especially at low application rates and concentrations, is not entirely satisfactory in all fields of application.
Accordingly, the present invention provides novel methoximinomethyloxadiazines of formula (I),
wherein
Z represents cycloalkyl, aryl, aralkyl, heterocyclyl or heterocycloalkyl, which are optionally substituted,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
x represents a halogen atom or a halogen atom,
L1、L2、L3and L4Are identical or different and each independently represents hydrogen, halogen, cyano, nitro or represents alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each of which is optionally substituted by halogen.
In each definition, a saturated or unsaturated hydrocarbon chain, such as alkyl, alkanediyl, alkenyl or alkynyl, includes the case where a heteroatom is bonded, such as in alkoxy, alkylthio or alkylamino, each being straight-chain or branched.
Aryl represents an aromatic, mono-or polycyclic hydrocarbon ring, such as phenyl, naphthyl, anthryl or phenanthryl, preferably phenyl or naphthyl, in particular phenyl.
Heterocyclyl represents saturated or unsaturated, and also aromatic, cyclic compounds in which at least one ring atom is a heteroatom, i.e. an atom other than carbon. If the ring contains multiple heteroatoms, they may be the same or different. Preferred heteroatoms are oxygen, nitrogen or sulfur. If the ring contains multiple oxygen atoms, they are not adjacent. If appropriate, the ring compounds form, together with other carbocyclic or heterocyclic, fused or bridged rings, polycyclic ring systems. Preference is given to monocyclic or bicyclic ring systems, in particular monocyclic or bicyclic aromatic ring systems.
Cycloalkyl represents saturated carbocyclic ring compounds which may optionally form, together with other carbocyclic, fused or bridged rings, polycyclic ring systems.
Furthermore, it has now been found that novel methoximinomethyloxadiazines of general formula (I) can be obtained as follows:
a) if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, reacting 3- (2-hydroxyphenyl) -3-methoxyiminomethyloxadiazines of the general formula (II) with substituted halogenopyrimidines of the general formula (III),
wherein,
L1、L2、L3and L4Each as defined above, is preferably a mixture of,wherein,
z, Q and X are each as defined above,
Y1represents halogen, or
b) If appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, with a ring compound of the formula (V),wherein,
X、L1、L2、L3and L4Each as defined above, is preferably a mixture of,
Y2represents a halogen atom or a halogen atom,
Z-Q-H (V) wherein,
z and Q are each as defined above.
Finally, it has been found that the novel methoximinomethyloxadiazines of the general formula (I) have very strong fungicidal activity.
The compounds of the invention may exist in different possible isomeric forms, in particular mixtures of stereoisomers such as E and Z isomers. The invention claims the E and Z isomers and any mixture of these isomers.
The present invention preferably provides compounds of the general formula (I) as defined below, in which
Z represents cycloalkyl or cycloalkylalkyl having in each case 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety and in each case optionally mono-to penta-substituted by halogen or alkyl,
represents heterocyclyl or heterocyclylalkyl having from 3 to 7 ring members each and from 1 to 4 carbon atoms in the alkyl moiety and each being optionally substituted by halogen or alkyl having from 1 to 4 carbon atoms, or
Represents aryl or arylalkyl each having from 6 to 10 carbon atoms in the aryl moiety and from 1 to 4 carbon atoms in the alkyl moiety and each being optionally mono-to tetrasubstituted by identical or different substituents, the possible substituents preferably being selected from:
halogen, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl,
alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl, each having 1 to 8 carbon atoms and each being straight-chain or branched,
alkenyl or alkenyloxy having in each case 2to 6 carbon atoms and in each case straight-chain or branched,
haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms and in each case straight-chain or branched,
halogenoalkenyl or halogenoalkenyloxy having in each case 2to 6 carbon atoms and 1 to 11 identical or different halogen atoms and in each case straight-chain or branched,
alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, alkenylcarbonyl or alkynylcarbonyl having from 1 to 6 carbon atoms in the hydrocarbon-based moiety concerned and each being straight-chain or branched,
cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms,
alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, each of which is doubly linked and each is optionally mono-to tetrasubstituted identically or differently, by substituents selected from the group consisting of fluorine, chlorine, oxo, methyl, trifluoromethyl and ethyl, or
A group of the formula:
wherein,
A1represents hydrogen or hasAlkyl of 1 to 4 carbon atoms or cycloalkyl of 3 to 6 carbon atoms, and
A2represents hydroxyl, amino, methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino, dialkylamino, having 1 to 4 carbon atoms in the alkyl chain in question,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
x represents fluorine, chlorine or bromine, preferably fluorine or chlorine, in particular fluorine, and
L1、L2、L3and L4Are identical or different and each independently represent hydrogen, halogen, cyano, nitro, or represent alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each having 1 to 6 carbon atoms and each being optionally substituted by 1 to 5 halogen atoms, preferably represents hydrogen or methyl, in particular represents hydrogen.
The invention relates in particular to compounds of the general formula (I) as defined below, in which
Z represents cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally mono-to pentasubstituted by fluorine, chlorine, methyl or ethyl,
represents thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl or furylmethyl, each of which is optionally substituted by methyl, ethyl, fluorine, chlorine or bromine, or
Represents phenyl or benzyl, each of which is optionally mono-to tetrasubstituted by identical or different substituents, the possible substituents preferably being selected from:
fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl,
methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxymethyl,
methoxy, ethoxy, n-or i-propoxy,
methylthio, ethylthio, n-or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl,
a methyl-aminomethyl group, a dimethyl-aminomethyl group,
vinyl, allyl, 2-methallyl, propen-1-yl, butenyl, propargyl, vinyloxy, allyloxy, 2-methallyloxy, propen-1-yloxy, butenyloxy, propargyloxy,
a trifluoromethyl group and a trifluoroethyl group,
difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy, 2-chloro-1, 1, 2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl,
methylamino, ethylamino, n-or i-propylamino, dimethylamino or diethylamino,
acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl or propioyl,
a cyclopentyl group and a cyclohexyl group,
propylene glycol, ethyleneoxy, methylenedioxy, ethylenedioxy, each of which is doubly linked and each of which is optionally mono-to tetrasubstituted identically or differently by substituents from the group consisting of fluorine, chlorine, oxo, methyl and trifluoromethyl, or
A group of the formula:
wherein,
A1represents hydrogen or methyl, and
A2represents hydroxy, methoxy, ethoxy, amino, methylamino, methyl, phenyl or benzyl,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
x represents fluorine or chlorine, in particular fluorine, and
L1、L2、L3and L4Are identical or different and each independently represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxy, ethoxy, n-or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, preferably represents hydrogen or methyl, in particular represents hydrogen.
The general or preferred definitions of the radicals mentioned above apply not only to the end products of the formula (I) but also correspondingly to the starting materials and intermediates required in each case for the preparation.
The definitions of the radicals given in particular for these radicals in the combinations or preferred combinations of radicals in question can also be substituted, independently of the combination given in each case, by definitions of radicals of other preferred ranges.
The formula (II) provides a general definition of the 3- (2-hydroxyphenyl) -3-methoxyiminomethyloxadiazines required as starting materials for carrying out the process a) according to the invention. In the formula (II), L1、L2、L3And L4Preference or particular meanings have already been given to L as preferred or particular meanings in the description of the compounds of the formula (I) according to the invention1、L2、L3And L4Those meanings given.
The starting materials of the formula (II) are novel and also form part of the subject matter of the present invention.
They are obtained by the following process c): if appropriate in the presence of a diluent and if appropriateWhen reacting the benzofurandione dioximes of the general formula (VI) with ammonia under elevated pressure,wherein
L1、L2、L3And L4Each as defined above, is capable of,
Y3represents halogen, alkylsulfonyl or arylsulfonyl.
The formula (VI) provides a general definition of the benzofurandione dioximes required as starting materials for carrying out the process c) according to the invention. In the formula (VI), L1、L2、L3And L4Each preferably or in particular having the meanings indicated as preferred or particular in the description of the compounds of the formula (I) according to the invention for L1、L2、L3And L4Those meanings given. Y is3Represents halogen, preferably chlorine or bromine, or represents alkylsulfonyl or arylsulfonyl, preferably methylsulfonyl, benzylsulfonyl or tolylsulfonyl.
The starting materials of the formula (VI) are novel and also form part of the subject matter of the present invention.
They are obtained by the following process d): if appropriate in the presence of a diluent and if appropriate in the presence of a base, with alkyl-or aryl-sulfonyl chlorides or halogenating agents,wherein
L1、L2、L3And L4Each as defined above.
The formula (VII) provides a general definition of the hydroxyethylbenzofurandione dioximes required as starting materials for carrying out the process d) according to the invention. In the formula (VII), L1、L2、L3And L4Each preferably or in particular having the meanings indicated as preferred or particular in the description of the compounds of the formula (I) according to the invention for L1、L2、L3And L4Those meanings given.
The starting material of formula (VII) can be obtained, for example, by the following process: optionally substituted benzofuranones (X) (see, for example, chem. be., 30(1897), 1081) are first reacted with methoxyamine to give benzofuranone oximes (IX), the benzofuranone oximes (IX) are then nitrosated with an alkyl nitrite and the resulting dioximes (VII) are finally alkylated with, for example, ethylene oxide (see also preparation examples):
furthermore, alkyl-or aryl-sulfonyl chlorides or halogenating agents are required for carrying out process d) according to the invention. Preferred alkyl-or aryl-sulfonyl chlorides are methyl-, ethyl-, phenyl-or tolyl-sulfonyl chlorides. Suitable halogenating agents are all those which can be used to replace the hydroxyl group attached to the carbon atom by halogen. Examples include: phosgene, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride or thionyl bromide.
The formula (III) provides a general definition of the halopyrimidines which are also required as starting materials for carrying out the process a) according to the invention. In this formula (III), Z, Q and X each preferably or in particular have those meanings which have already been given as preferred or particular meanings for Z, Q and X in the description of the compounds of the formula (I) according to the invention. Y is1Represents halogen, preferably fluorine or chlorine.
The starting materials of the formula (III) are known (see, for example, DE-A4340181; chem. Ber., 90(1957)942, 951) and/or they can be prepared by known methods, for example by reacting trihalopyrimidines of the formula (XI) (see below) with cyclic compounds of the formula (V) (see below).
The formula (IV) provides a general definition of the phenoxypyrimidines required as starting materials for carrying out the process b) according to the invention. In the formula (IV), X, L1、L2、L3And L4Each having the preferred or special meanings indicated as preferred or special in the description of the compounds of the formula (I) according to the invention X, L1、L2、L3And L4Those meanings given. Y is2Represents halogen, preferably fluorine or chlorine.
The starting materials of the formula (IV) are novel and also form part of the subject matter of the present invention.
The phenoxypyrimidines of formula (IV) are obtained by process e) as follows: if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, reacting a 3- (2-hydroxyphenyl) -3-methoxyiminomethyloxadiazine of the formula (II) with a trihalopyrimidine of the formula (XI),
x, Y therein1And Y2Identical or different, each represents halogen.
The 3- (2-hydroxyphenyl) -3-methoxyiminomethyloxadiazines of the general formula (II) required as starting materials for carrying out process e) according to the invention have already been described in connection with the description of process a) according to the invention.
The formula (XI) provides a general definition of the trihalopyrimidines which are also required as starting materials for carrying out the process e) according to the invention. In this formula (XI), X, Y1And Y2Each represents halogen, preferably fluorine or chlorine.
Trihalopyrimidines of the formula (XI) are known and/or they can be prepared by known methods (see, for example, Chesterfield et al, J.chem.Soc., 1955; 3478, 3480).
The formula (V) provides a general definition of the ring compounds which are also required as starting materials for carrying out the process b) according to the invention. In this formula (V), Z and Q each preferably or in particular have those meanings which have already been given for Z and Q as preferred or particular meanings in the description of the compounds of the formula (I) according to the invention.
The ring compounds of formula (V) are known chemicals for synthesis or can be prepared by known methods.
Suitable diluents for carrying out the processes a), b) and e) according to the invention are all inert organic solvents. They preferably include ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n-or iso-butyronitrile or benzonitrile; amides, such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-N-formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; sulfoxides, such as dimethyl sulfoxide; or sulfones, such as sulfolane.
Suitable diluents for carrying out the process c) according to the invention are all inert organic solvents. They preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane or anisole; amides, such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; sulfoxides, such as dimethyl sulfoxide; sulfones, such as sulfolane; alcohols, for example methanol, ethanol, n-or i-propanol, n-, i-, s-or t-butanol, ethylene glycol, propane-1, 2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
Suitable diluents for carrying out the process d) according to the invention are all inert organic solvents. They preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane or anisole; ketones, such as acetone, butanone or methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n-or iso-butyronitrile or benzonitrile; amides, such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-N-formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate; sulfoxides, such as dimethyl sulfoxide; sulfones, such as sulfolane.
The processes a), b) and e) according to the invention are, if appropriate, carried out in the presence of suitable acid acceptors. Suitable acid acceptors are all customary inorganic or organic bases. They preferably include alkaline earth or alkali metal hydrides, hydroxides, alcoholates, carbonates or bicarbonates, such as sodium hydride, sodium amide, potassium tert-butylate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium bicarbonate or sodium bicarbonate.
If appropriate, the process d) according to the invention is carried out in the presence of a suitable acid acceptor. Suitable acid acceptors are all customary inorganic or organic bases. They preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butylate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium bicarbonate, sodium bicarbonate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), Diazabicyclononene (DBN) or Diazabicycloundecene (DBU).
Suitable catalysts for carrying out the processes a), b) and e) according to the invention are all copper (I) salts, such as copper (I) chloride, copper (I) bromide or copper (I) iodide.
When carrying out the processes a), b) and e) according to the invention, the reaction temperatures can be varied within a relatively wide range. Generally, the reaction is carried out at a temperature between-20 ℃ and 100 ℃, preferably between-10 ℃ and 80 ℃.
When carrying out the process c) according to the invention, the reaction temperatures can be varied within a relatively wide range. Generally, the reaction is carried out at a temperature between 20 ℃ and 250 ℃, preferably between 50 ℃ and 150 ℃.
When carrying out the process d) according to the invention, the reaction temperatures can be varied within a relatively wide range. Generally, the reaction is carried out at a temperature between-20 ℃ and 80 ℃, preferably between-10 ℃ and 40 ℃.
To carry out the process a) according to the invention for preparing the compounds of the general formula (I), from 0.5 to 15mol, preferably from 0.8 to 8mol, of substituted halogenopyrimidines of the formula (III) are generally used per mole of 3- (2-hydroxyphenyl) -3-methoxyiminomethyloxadiazine of the formula (II).
To carry out the process b) according to the invention for preparing the compounds of the general formula (I), from 0.5 to 15mol, preferably from 0.8 to 8mol, of ring compound of the formula (V) are generally used per mole of phenoxypyrimidine of the formula (IV).
To carry out the process d) according to the invention for preparing the compounds of the formula (VI), in general from 1 to 15mol, preferably from 2to 8mol, of alkyl-or aryl-sulfonyl chloride or halogenating agent are employed per mole of hydroxyethylbenzofurandione dioxime of the formula (VII).
To carry out the process e) according to the invention for preparing the compounds of the general formula (IV), in general from 1 to 15mol, preferably from 2to 8mol, of trihalopyrimidine of the formula (XI) are employed per mole of 3- (2-hydroxyphenyl) -3-methoxyiminomethyloxadiazine of the formula (II).
The processes a), b), d) and e) according to the invention are generally carried out at atmospheric pressure. However, it is also possible to work under elevated or reduced pressure- -generally between 0.1 and 10 bar.
The process c) according to the invention is generally carried out at elevated pressure. The process is preferably carried out at a pressure of from 2to 100 bar, in particular from 3 to 50 bar.
In general, working up of these reactions and isolation of the reaction products are carried out in a customary manner (cf. also the preparation examples).
The active compounds according to the invention have a strong microbicidal action and can be used for controlling undesirable microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
Fungicides in crop protection are used for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
Bactericides can be used in crop protection for controlling Pseudomonadaceae (pseudomonas adaceae), Rhizobiaceae (Rhizobiaceae), Enterobacteriaceae (Enterobacteriaceae), Corynebacteriaceae (Corynebacteriaceae) and Streptomycetaceae (Streptomycetaceae).
By way of example, mention may be made of some pathogens of fungal and bacterial diseases under the generic names mentioned above, without this being limiting: xanthomonas species (Xanthomonas), such as Xanthomonas oryzae var (Xanthomonas campestris pv. oryzae); pseudomonas species (Pseudomonas), such as Pseudomonas syringae (Pseudomonas syringae) Pseudomonas syringae var (Pseudomonas syringae pv. lachrymans); erwinia species (Erwinia), such as Erwinia amylovora (Erwinia amylovora); pythium species (Pythium), such as Pythium ultimum; phytophthora species (Phytophthora), such as Phytophthora infestans (Phytophthora infestans); pseudoperonospora species (Pseudoperonospora), such as Pseudoperonospora humuli (Pseudoperonospora humuli) or Pseudoperonospora cubensis (Pseudoperonospora cubensis); plasmopara species, such as Plasmopara viticola (Plasmopavaticola); species of the genus Bremia (Bremia), such as Bremia lactucae (Bremia lactucae); peronospora species (Peronospora), such as Peronospora pisi (Peronospora pisi) or Peronospora brassicae (Peronospora brassicae); erysiphe species (Erysiphe), such as Erysiphe graminis (Erysiphe graminis); species of the genus Sphaerotheca (e.g., Sphaerotheca fuliginea); podosphaera species (Podosphaera), such as Podosphaera leucotricha (Podosphaera leucotricha); venturia species (Venturia), such as Venturia inaequalis; pyrenophora species (Pyrenophora), such as Pyrenophora teres or Pyrenophora graminea (Pyrenophora graminea) (conidia form: Helminthosporium (Drechslera), synonym: Helminthosporium (Helminthosporium)); a genus of the genus Sporotrichum (Cochliobolus), such as, for example, Cochliobolus graminis (Cochliobolus sativus) (conidia form: Helminthosporium (Drechslera), synonym: Helminthosporium (Helminthosporium)); species of the genus unicellular rust (Uromyces), such as, for example, puccinia verrucosa (Uromyces apendiculus); puccinia species (Puccinia), such as Puccinia recondita (Puccinia recondita); sclerotinia species (sclerotiotinia), such as Sclerotinia sclerotiorum (sclerotiniotiorum); tilletia species (Tilletia), such as Tilletia tritici (Tilletia acaries); ustilago species (Ustilago), such as Ustilago nuda (Ustilago nuda) or Ustilago avenae (Ustilago avenae); pellicularia species (Pellicularia), such as, for example, Pellicularia azonian (Pellicularia sasakii); pyricularia species, such as Pyricularia oryzae; fusarium species (Fusarium), such as Fusarium culmorum (Fusarium culmorum); botrytis species (Botrytis), such as Botrytis cinerea (Botrytis cinerea); septoria species (Septoria), such as Septoria nodorum (Septoria nodorum); leptosphaeria species (Leptosphaeria), such as Leptosphaeria nodorum (Leptosphaeria nodorum); cercospora species (Cercospora), such as Cercospora canescens; alternaria species (Alternaria), such as Alternaria brassicae (Alternaria brassicae); pseudocercospora species (pseudocercospora), for example pseudocercospora herpotrichoides.
The fact that the plants have good tolerance to the active compounds at the concentrations required for controlling plant diseases allows the treatment of the aerial parts of the plants, of the propagation of rhizomes and seeds, and of the soil.
The active compounds according to the invention can be employed particularly successfully for controlling cereal diseases, for example against the species Leptosphaeria (Leptosphaeria), Puccinia (Puccinia) and Fusarium (Fusarium); for controlling diseases in the growth and cultivation of fruits and vegetables, such as species of anti-Venturia (Venturia), Sphaerotheca (Sphaerotheca) and Plasmopora; for the control of rice diseases, for example against Pyricularia species.
Furthermore, the compounds of the invention can also be used to increase crop yield. They also have reduced toxicity and are well tolerated by crops.
Depending on their specific physical and/or chemical properties, the active compounds can be formulated into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cold and hot fogging formulations.
These formulations can be prepared in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure and/or solid carriers, optionally with the use of surfactants, that is, emulsifiers and/or dispersants and/or foam formers. If the extender used is water, it is also possible to use, for example, organic solvents as cosolvents. Suitable liquid solvents are mainly: aromatic compounds, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or ethylene glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gas extenders or carriers refer to liquids that are gases at ambient temperature and pressure, such as aerosol propellants, for example butane, propane, nitrogen and carbon dioxide; suitable solid carriers are, for example: ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly dispersed silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and crushed natural minerals such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of organic and inorganic powders, and granules of organic substances such as: such as sawdust, coconut shells, corn cobs and tobacco stems; suitable emulsifiers and/or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: such as lignin sulfite waste liquor and methyl cellulose.
In the formulation, viscosity-increasing agents such as carboxymethylcellulose, natural and synthetic polymers in powder, granule or latex form, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalins and lecithins, and synthetic phospholipids may be used. Other possible additives are mineral and vegetable oils.
It is also possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
In general, the formulations contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90%.
Depending on their specific physical and/or chemical properties, the active compounds can be formulated into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cold and hot fogging formulations.
The active compounds according to the invention can be used as such or in their formulations also in admixture with other known fungicides, bactericides, acaricides, nematicides or insecticides, for example to broaden the spectrum of action or to prevent the development of resistance. In many cases this leads to a synergistic effect, i.e. the activity of the mixture exceeds the activity of the individual components.
Suitable ingredients for such mixtures are, for example, the following:
fungicides:
aldimorph, alanine phosphoric acid, potassium alanine phosphate, andoprim, trichlorfon, penconazole and azoxystrobin,
benalaxyl, iodocarboxin, benomyl, benzamacil, benzacryl-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin, bromuconazole, butylpyrimidine sulfonate, butrit,
lime sulphur, capsimycin, captafol, captan, carbendazim, carboxin, fenpyrone, fenpicloram, chlorofenazole, anisole, chloropicrin, chlorothalonil, ethephon, clozylacon, thiabendazole, cymoxanil, cyproconazole, cyprodinil, estericamide,
prochloraz, antifungal phenol, benzyl chloride triadimenol, dichlofluanid, pyridaben, niclosamide, diethofencarb, difenoconazole, pyrimethanil, dimethomorph, diniconazole-M, clomiprinil, diphenylamine, pyrithion, fenaminostrobin, dithianon, dodecamorpholine, dodine and hydrazone mycone,
kejunsan, epoxiconazole, ethiconazole, ethirimol and chlorpropham,
famoxadon, fenacet, fenarimol, fenbuconazole, furametpyr, meptyl, fenpiclonil, fenpropidin, fenpropimorph, triphenyltin acetate, triphenyltin, ferbam, ferimzone, fluazinam, flumetover, flucloxacillin, fluquinconazole, fluvozole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl-sodium, tetrachlorophthalide, fuberidazole, furametpyr, difuracil, furametpyr,
the biguanide zinc acetate salt is a salt of zinc,
hexachlorobenzene, hexaconazole, methylhydroxyisoxazole,
imazalil, imibenconazole, iminoctadine octanephsylate, iminoctadine acetate, edocarb, ipconazole, iprobenfos, iprampicin, isoprothiolane, isovaledione,
kasugamycin, kresoxim-methyl, copper preparations, such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, quinolinone and bordeaux mixture,
a binary mixture, mancozeb, maneb, meferimzone, mepanipyrim, mefenoxam, metalaxyl, metconazole, sulbactam, furametpyr, metiram, fenclofenamide, tiadinil, milomycin, myclobutanil, metconazole,
thiram, iprodione, fluoropyrimidinol,
methylfuroamide, oxanamide, oxamocarb, quinconazole, oxycarboxin, oxyphenanthin,
paclobutrazol, pefurazoate, penconazole, pencycuron, oryzophos, isoprothiolane, pimaricin, piperidinin, polyoxin, polyoxorim, probenazole, prochloraz, dimetachlone, propamocarb, propanoosine-sodium, propiconazole, propineb, fenamiphos, pyribenzoxim, pyrimethanil, pyroquilon, clopyralid,
quinconazole, quintozene,
sulphur and a sulphur preparation, wherein the sulphur is selected from the group consisting of,
tebuconazole, phthalic acid, tetrachloronitrobenzene, cyclonene, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofos-methyl, triadimefon, triadimenol, triabutil, pyrazoxazine, trichlamide, tricyclazole, morpholine, triflumizole, triforine, triticonazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, thiabendazole, thiabenda,
The compound of the uniconazole is shown in the specification,
paddy powder, ethephon, dimethoate and dimethenazole,
cyanamide, zineb, ziram, and
Dagger G，
OK-8705，
OK-8801，
alpha- (1, 1-dimethylethyl) -beta- (2-phenoxyethyl) -1H-1, 2, 4-triazole-1-ethanol,
Alpha- (2, 4-dichlorophenyl) -beta-fluoro-b-propyl-1H-1, 2, 4-triazole-1-ethanol,
Alpha- (2, 4-dichlorophenyl) -beta-methoxy-a-methyl-1H-1, 2, 4-triazole-1-ethanol,
A- (5-methyl-1, 3-dioxane-5-yl) - β - [ [4- (trifluoromethyl) -phenyl ] -methylene ] -1H-1, 2, 4-triazole-1-ethanol,
(5RS, 6RS) -6-hydroxy-2, 2, 7, 7-tetramethyl-5- (1H-1, 2, 4-triazol-1-yl) -3-octanone,
(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{ 2-methyl-1- [ [ [1- (4-methylphenyl) ethyl ] amino ] carbonyl ] propyl } -carbamic acid 1-isopropyl ester,
1- (2, 4-dichlorophenyl) -2- (1H-1, 2, 4-triazol-1-yl) ethanone-O- (phenylmethyl) -oxime,
1- (2-methyl-1-naphthyl) -1H-pyrrole-2, 5-dione,
1- (3, 5-dichlorophenyl) -3- (2-propenyl) -2, 5-pyrrolidinedione,
1- [ (diiodomethyl) -sulfonyl ] -4-methyl-benzene,
1- [ [2- (2, 4-dichlorophenyl) -1, 3-dioxolan-2-yl ] -methyl ] -1H-imidazole,
1- [ [2- (4-chlorophenyl) -3-phenyloxiranyl ] -methyl ] -1H-1, 2, 4-triazole,
1- [1- [2- [ (2, 4-dichlorophenyl) methoxy ] phenyl ] vinyl ] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6' -dibromo-2-methyl-4 '-trifluoromethoxy-4' -trifluoromethyl-1, 3-thiazole-5-carboxanilide,
2, 2-dichloro-N- [1- (4-chlorophenyl) ethyl ] -1-ethyl-3-methyl-cyclopropanecarboxamide,
2, 6-dichloro-5- (methylthio) -4-pyrimidyl thiocyanate,
2, 6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,
2, 6-dichloro-N- [ [4- (trifluoromethyl) phenyl ] methyl ] -benzamide,
2- (2, 3, 3-triiodo-2-propenyl) -2H-tetrazole,
2- [ (1-methylethyl) sulfonyl ] -5- (trichloromethyl) -1, 3, 4-thiadiazole,
2- [ [ 6-deoxy-4-O- (4-O-methyl-beta-D-glucopyranosyl) -a-D-glucopyranosyl ] -amino ] -4-methoxy-1H-pyrrolo [2, 3-D ] pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) -glutaronitrile,
2-chloro-N- (2, 3-dihydro-1, 1, 3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide,
2-chloro-N- (2, 6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,
2-phenylphenol (OPP),
3, 4-dichloro-1- [4- (difluoromethoxy) -phenyl ] -1H-pyrrole-2, 5-dione,
3, 5-dichloro-N- [ cyano- [ (1-methyl-2-propynyl) oxy ] methyl ] -benzamide,
3- (1, 1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl ] -pyridine,
4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide,
4-methyl-tetrazolo [1, 5-a ] -quinazolin-5 (4H) -one,
8- (1, 1-dimethylethyl) -N-ethyl-N-propyl-1, 4-dioxaspiro [4.5] decan-2-methanamine,
8-hydroxyquinoline sulfate,
9H-xanthene-2- [ (phenylamino) -carbonyl ] -9-carboxylic acid hydrazine,
Bis- (1-methylethyl) -3-methyl-4- [ (3-methylbenzoyl) oxy ] -2, 5-thiophenedicarboxylate,
Cis-1- (4-chlorophenyl) -2- (1H-1, 2, 4-triazol-1-yl) -cycloheptanol,
Cis-4- [3- [4- (1, 1-dimethylpropyl) -phenyl ] -2-methylpropyl ] -2, 6-dimethyl-morpholine hydrochloride,
[ (4-chlorophenyl) -azo ] -cyanoacetic acid ethyl ester,
Potassium bicarbonate,
Methyl tetrathiol-sodium salt,
1- (2, 3-dihydro-2, 2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylic acid methyl ester,
N- (2, 6-dimethylphenyl) -N- (5-isoxazolecarbonyl) -DL-alanine methyl ester,
N- (chloroacetyl) -N- (2, 6-dimethylphenyl) -DL-alanine methyl ester,
N- (2, 3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexanecarboxamide,
N- (2, 6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) -acetamide,
N- (2, 6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) -acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-cyclohexylphenyl) -1, 4, 5, 6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1, 4, 5, 6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) -acetamide,
N- (6-methoxy) -3-pyridyl) -cyclopropanecarboxamide,
N- [2, 2, 2-trichloro-1- [ (chloroacetyl) -amino ] -ethyl ] -benzamide,
N- [ 3-chloro-4, 5-bis (2-propynyloxy) -phenyl ] -N' -methoxy-methylaminoamide,
N-formyl-N-hydroxy-DL-alanine sodium salt,
O, O-diethyl [2- (dipropylamino) -2-oxoethyl ] -ethylthiophosphoramide,
O-methyl-S-phenyl-propyl-thiophosphoramide,
S-methyl 1, 2, 3-benzothiadiazole-7-thiocarboxylic ester,
Spiro [2H ] -1-benzopyran-2, 1 ' (3 ' H) -isobenzofuran ] -3 ' -one,
a bactericide:
gossypol, antifungal phenol, chlordine, thiram, kasugamycin, isothiazolinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, phthalein, copper sulfate, and other copper preparations.
Insecticide/acaricide/nematicide:
abamectin, acephate, fluthrin, boll-bell-carbofuran, aldicarb, alpha-cypermethrin, amitraz, avermectin, AZ 60541, toosendanin, ethyl valthion, azocyclotin,
bacillus thuringiensis, 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensulam, alpha-cyfluthrin, bifenthrin, fenobucarb, brofenprox (brofenprox), bromophos, pendimethalin, buprofezin, butoxycarb, butyrpyridaben,
cadusafos, carbaryl, carbofuran, thiophosphoryl, carbosulfan, cartap, oxamyl, phosphorus oxychloride, chlorfenvinphos, chlorfluazuron, chlormephos, N- [ (6-chloro-3-pyridyl) -methyl ] -N' -cyano-N-methyl-acetimidamide, chlorpyrifos-methyl, cis-resmethrin, cyhalothrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
deltamethrin, methyl systemic phosphorus, isosystemic phosphorus II, chlordiazuron, dinosaur, clomiphos, dichlorvos, dichliphos, chlorothalofos, ethion, flufenoxuron and dimethoate,
chlorfenvinphos, dioxin and disulfoton,
kewensan, emamectin, esfenvalerate, pirimicarb, ethion, ethofenprox, ethoprophos, etrimfos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenoxycarb, fenpropathrin, fenpyrd, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, pyridaben, flucycloxuron, flucythrinate, flufenoxuron, bifenthrin (flufenprox), flucyanmethrin, fonofos, difructon, fosthiazate, brofenprox (furfenprox), furdiocarb,
hexachloro-cyclohexane, heptenophos, hexaflumuron and hexythiazox,
imidacloprid, iprobenfos, chlorzophos, isopropylamine, isoprocarb, oxazaphosphorine and ivermectin,
lambda-cyhalothrin, lufenuron,
malathion, phosmet, metophos, fenthion sulfoxide, metaldehyde, chlorfenvinphos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, methoxidectin, chlorphos, chlorp,
Dibromophosphate, NC 184, nitenpyram,
omethoate, oxamyl, SULPHUS,
parathion, methyl parathion, permethrin, phenthoate, phorate, phoxim, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos-methyl, pirimiphos, profenofos, propamocarb, propoxur, low toxicity pho-phos, pomade, pymetrozin, pyrazofos, pyridaphenthion, resmethrin, pyrethrin, pyridaben, pyriminobac-methyl, pyriproxyfen,
the quinalphos is a compound of quinalphos,
salithion, cadusafos, silafluofen, sulfotepa, meprobamate,
tebufenozide, tebufenpyrad, terbufos, tefluthrin, fenthion, terbufos, fenpropathrin, fenthiofenox, thiodicarb, ketoxycarb, fosetyl-methyl, quinclofos, thuringiensis, tetrabromthrin, phencyazoate, triazophos, triazuron, trichlorfon, chlorfluazuron, methimazole, methiocarb,
thiofenthion, dimethylcarbofuran, xylylcarb, zetamethrin.
Mixtures with other known active compounds, such as herbicides or fertilizers, and growth regulators are also possible.
The active compounds according to the invention can be used as such, in the form of their formulations or in the use forms prepared from such formulations, such as directly usable solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They may be used in conventional manner, for example by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active compounds by the ultra-low volume method or to inject the active compound preparation or the active compound itself into the soil. The seeds of the plants may also be treated.
When the active compounds according to the invention are used as fungicides, the application dosage can vary within a relatively wide range, depending on the type of application. In the treatment of plant parts, the active compounds are generally applied in a dose of between 0.1 and 10,000g/ha, preferably between 10 and 1000 g/ha. In the treatment of seed, the active compounds are generally applied in a dose of between 0.001 and 50g/kg of seed, preferably between 0.01 and 10g/kg of seed. In the treatment of soil, the active compounds are generally applied in a dose of between 0.1 and 10,000g/ha, preferably between 1 and 5000 g/ha.
Preparation examples
Example 1
Method b)
To a solution of 0.7g (2mmol) of 3- {1- [2- (4, 5-difluoropyrimidin-6-yloxy) phenyl ] -1- (methoxyimino) methyl } -5, 6-dihydro-4H-1, 2, 4-oxadiazine in 30ml of acetonitrile at 20 ℃ are added first 0.33g (2mmol) of 2, 3-dichlorophenol and then 0.33g (2.4mmol) of potassium carbonate. The mixture was stirred overnight, filtered, added to 150ml of ethyl acetate and washed with water. Finally, the organic phase is dried over sodium sulfate and concentrated under reduced pressure to give a viscous oil which slowly crystallizes. 0.9g (91.8% of theory) of 3- {1- [2- (4- (2, 3-dichlorophenoxy) -5-fluoropyrimidin-6-yloxy) phenyl ] -1- (methoxyimino) methyl } -5, 6-dihydro-4H-1, 2, 4-oxadiazine are obtained.
HPLC：log：3.45。
By the process of example 1, following the general description of the preparation processes a) and b) according to the invention, the compounds of the formula (I-a) listed in Table 1 below are likewise obtained:
table 1:
Table 1:
table 1:
table 1:
*) The logP value is determined by HPLC (gradient method, acetonitrile/0.1% aqueous phosphoric acid) according to EEC Directive 79/831 Annex V.A8.
| examples | Q | Z | logP* |
| 2 | O | 3-chloro-2-methylphenyl | 3,52 |
| 3 | O | 2-chlorophenyl group | 3,02 |
| 4 | O | 2, 3-dimethylphenyl | 3,29 |
| 5 | O | 3-chlorophenyl group | 3,23 |
| 6 | O | 4-chlorophenyl group | 3,23 |
| 7 | O | 2-vinylphenyl | 3,38 |
| 8 | O | 2-tolyl radical | 3,01 |
| 9 | O | 2-bromophenyl radical | 3,08 |
| 10 | O | 2-fluorophenyl group | 2,85 |
| 11 | O | 2-ethylphenyl radical | 3,32 |
| 12 | O | 3-tert-butylphenyl group | 3,96 |
| 13 | O | 2-isopropylphenyl | 3,59 |
| 14 | O | 2-methoxyphenyl radical | 2,70 |
| 15 | O | 2, 4-dimethylphenyl | 3,38 |
| 16 | O | 2, 5-dimethylphenyl | 3,35 |
| 17 | O | 2-cyclopentylphenyl | 4,01 |
| 18 | O | 2-chloro-5-methylphenyl | 3,35 |
| 19 | O | 2, 6-dimethylphenyl | 3,29 |
| 20 | O | 3-tolyl radical | 3,10 |
| 21 | O | 4-tolyl radical | 3,08 |
| 22 | O | 2-tert-butylphenyl | 3,84 |
| examples | Q | Z | logP* |
| 54 | S | 2-chlorophenyl group | |
| 55 | S | 2, 4-dichloro-3-trifluoromethylphenyl | 4.30 |
| 56 | S | 4-chloro-3-trifluoromethylphenyl | |
| 57 | S | Cyclohexyl radical | 4.01 |
| 58 | S | Benzyl radical | 3.42 |
| 59 | O | 2-chloro-3-methylphenyl radical | 3.34 |
| 60 | O | 2-ethylsulfanylmethyl phenyl | 3.40 |
| 61 | O | 2-methoxymethylphenyl group | 2.74 |
| 62 | O | 2-ethoxymethylphenyl radical | 3.04 |
| 63 | O | 2-methylthiophenyl | 2.95 |
| 64 | O | 2-ethylthiophenyl | 3.26 |
Preparation of the starting Material of formula (II)
Example (II-1)
Method c)
1.26g (4mmol) of benzofuran-2, 3-dione 2- [ O- (2-methylsulfonyloxyethyl) oxime ]3- (O-methyloxime) are initially introduced into 15ml of methanol in an autoclave, 2.5g (147mmol) of ammonia are then condensed in, and the autoclave is heated at 100 ℃ under autogenous pressure for 16 hours. The autoclave was cooled to 20 ℃ and the reaction mixture was taken out and the solvent was distilled off under pressure. Finally, the residue was stirred with water and the resulting white solid was filtered off and dried overnight in a drying chamber. 0.9g (96% of theory) of 3- {1- [ 2-hydroxyphenyl ] -1- (methoxyimino) methyl } -5, 6-dihydro-4H-1, 2, 4-oxadiazine are obtained.
1H-NMR：δ＝3.57(m，2H)；3.98(s，3H)；4.05(m，2H)ppm
Preparation of the starting Material of formula (III)
Example (III-1)
A solution of 42.4g (0.45mol) of phenol and 50.4g (0.45mol) of potassium tert-butoxide in 400ml of tetrahydrofuran is added dropwise at 0 ℃ to a solution of 80g (0.6mol) of 4, 5, 6-trifluoropyrimidine in 1 l of tetrahydrofuran. After the addition was complete, the reaction mixture was stirred at 0 ℃ for 30 minutes, then poured into water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate, concentrated under reduced pressure and the residue is stirred with low-boiling petroleum ether. 63.8g (68.1% of theory) of 4-phenoxy-5, 6-difluoropyrimidine having a boiling point of 65-66 ℃ are obtained.
Preparation of the precursor
A mixture of 609g of potassium fluoride in 2.3 l of sulfolane was dried by evaporating off 500ml of liquid at 145 ℃ and 20 mbar. 1054g of 5-chloro-4, 6-difluoropyrimidine (DE-A3843558) and 25g of tetraphenylphosphonium chloride were added. A nitrogen pressure of 5bar was applied and the mixture was stirred at 240 ℃ for 24 hours, during which the pressure was increased to 11 bar. The reaction mixture was cooled to 80 ℃ and vented. The mixture was then slowly heated at atmospheric pressure and the product distilled. Once a bottom temperature of 200 ℃ has been reached, the pressure is reduced to 150mbar to accelerate the distillation and to give further product. This gives a total of 664g (70.7% of theory) of 4, 5, 6-trifluoropyrimidine with a boiling point of 86-87 ℃.
Preparation of the starting Material of formula (IV)
Example (IV-1)
Method e)
To a solution of 1.2g (5.1mmol) of 3- {1- [ 2-hydroxyphenyl ] -1- (methoxyimino) methyl } -5, 6-dihydro-4H-1, 2, 4-oxadiazine in 30ml of acetonitrile at 20 ℃ are added first 0.7g (5.1mmol) of 4, 5, 6-trifluoropyrimidine and then 1.4g (10.2mmol) of potassium carbonate. The mixture was stirred overnight, filtered, added to 150ml of ethyl acetate and washed with water. Finally, the organic phase is dried over sodium sulfate and concentrated under reduced pressure to give a viscous oil which slowly crystallizes. 1.4g (82% of theory) of 3- {1- [2- (4, 5-difluoropyrimidin-6-yloxy) phenyl ] -1- (methoxyimino) methyl } -5, 6-dihydro-4H-1, 2, 4-oxadiazine are obtained.
HPLC：log：1.97。
Preparation of the starting Material of formula (VI)
Example (VI-1)
3.2g (0.0135mol) of benzofuran-2, 3-dione 2- [ O- (2-hydroxyethyl) oxime ]3- (O-methyloxime) are initially taken in 100ml of dichloromethane and then mixed with 1.05ml (0.0135mol) of methanesulfonyl chloride at 20 ℃. After 15 minutes, 5.6ml (0.0406mol) of triethylamine were added to the mixture at 10 ℃ under ice cooling. Finally, the compound was warmed to 20 ℃ and stirred for 4.5 hours. The reaction mixture was then added to methyl tert-butyl ether, washed with water, dried over magnesium sulfate and concentrated under reduced pressure. 4.0g (94.2% of theory) of benzofuran-2, 3-dione 2- [ O- (2-methylsulfonyloxyethyl) oxime ]3- (O-methyloxime) are obtained as a white solid.
HPLC：logP：2.39。
Preparation of precursors of the formulae (VII), (VIII) and (IX)
Compound (IX-1)
6.7g (0.05mol) of benzofuran-3-one, 4.2g (0.05mol) of O-methylhydroxylamine hydrochloride and 4.1g (0.05mol) of sodium acetate in 50ml of methanol are heated under reflux for 3 hours. The solvent was evaporated off under reduced pressure, the reaction mixture was poured into water, extracted with ethyl acetate and the organic phase was washed with saturated aqueous sodium bicarbonate. The organic phase was dried over sodium sulfate and the solvent was evaporated off under reduced pressure. 7.27g (89.2% of theory) of crude furan-3-one O-methyloxime were obtained. For analysis, the product was distilled in a bulb at 2torr and 70 ℃ to give an oil. Both NMR and HPLC analysis indicated that the oil contained two isomers (79% isomer B and 21% isomer a).
1H-NMR Spectroscopy (DMSO-d)6(TMS): δ — 3.93(3H, isomer B); 3.93(3H, isomer A); 5.11(2H, isomer A); 5.16(2H, isomer B); 7.0-7.07 (2H); 7.39-7.45 (1H); 7.54/7.57(1H, isomer B); 7.95-8.02(1H, isomer A) ppm.
Compound (VIII-1)
3.92g (0.035mol) of potassium tert-butoxide are dissolved in 40ml of tert-butanol. This solution was mixed with a solution of 5.7g (0.035mol) benzofuran-3-one O-methyloxime and 7.2g (0.07mol) tert-butyl nitrite in 10ml tert-butanol. The mixture was stirred for 2 hours without cooling and then mixed with 20ml of a 2N aqueous hydrochloric acid solution. The crystallized product is filtered off, washed repeatedly with water and dried in a desiccator. This gave 3.19g (47.1% of theory) of benzofuran-2, 3-dione 3- (O-methyloxime) 2-oxime. According to HPLC analysis, the oil contained a mixture of two stereoisomers 86.33% of isomer a and 12.98% of isomer B.
1H-NMR Spectroscopy (DMSO-d)6(TMS): δ 4.10(3H, isomer B); 4.11(3H, isomer A); 7.21/7.24/7.26 (1H); 7.31/7.34 (1H); 7.51/7.53/7.56 (1H); 7.63/7.65(1H, isomer B); 8.02/8.05(1H, isomer A); 11.36(1H, isomer A); 11.75(1H, isomer B) ppm.
Compound (VII-1)
Method b)
264.3g (6.0mol) of ethylene oxide were introduced over a period of 85 minutes into a solution of 192.2g (1.0mol) of benzofuran-2, 3-dione 3- (O-methyloxime) 2-oxime in 2 l of water at 20 ℃. The solution was cooled to 5 ℃ and 70g (1.06mol) of granular potassium hydroxide were added, the temperature rising to 10 ℃ during the addition. Stirring is continued for 165 minutes without any further cooling and the precipitate formed is filtered off with suction, washed with portions of 500ml of ice-water and dried at 40 ℃ in a vacuum drying oven, whereby 143.0g (61% of theory) of benzofuran-2, 3-dione 2- [ O- (2-hydroxyethyl) oxime ]3- (O-methyloxime) are obtained as a mixture of the two stereoisomers.
HPLC：logP＝1.65(0.5％)；1.79(99.5％)。
Application examples
Example A
Leptosphaeria nodorum (wheat)/protective
Solvent: 25 parts by weight of N, N-dimethylacetamide
Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether
To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
In testing for protective activity, young plants are sprayed with the preparation of active compound at the stated application dose. After the spray dried, the plants were sprayed with a spore suspension of Leptosphaeria nodorum (Leptosphaerianodorum). The plants were kept in a greenhouse at 20 ℃ and 100% relative atmospheric humidity for 48 hours.
The plants were then placed in a greenhouse at a temperature of about 15 ℃ and a relative atmospheric humidity of 80%.
Evaluation was performed 10 days after inoculation. 0% means that the efficacy is comparable to the control, whereas 100% means that no infection is observed.
In this test, the substances according to the invention described in example (3) show an efficiency of 90% or more at an application rate of 250 g/ha.
Example B
Leaf rust (Puccinia) test (wheat)/therapeutic
Solvent: 25 parts by weight of N, N-dimethylacetamide
Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether
To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
In testing for therapeutic activity, seedlings were sprayed with a conidia suspension of Puccinia recondita (Puccinia recondita). The plants were placed in a culture chamber at 20 ℃ and 100% relative atmospheric humidity for 48 hours. The plants are then sprayed with the preparation of active compound at the stated dosage.
The plants were placed in a greenhouse at a temperature of about 20 ℃ and a relative atmospheric humidity of about 80% to promote the generation of leaf rust spots.
Evaluation was performed 10 days after inoculation. 0% means that the efficacy is comparable to the control, whereas 100% means that no infection is observed.
In this test, the substances according to the invention described in example (3) show an efficiency of 90% or more at an application rate of 250 g/ha.
Example C
Snow rot (Fusarium nivale (var. nivale)) test (wheat)/protective
Solvent: 25 parts by weight of N, N-dimethylacetamide
Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether
To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
In testing for protective activity, young plants are sprayed with the preparation of active compound at the stated application dose. After the spray coat has dried, the plants are sprayed with an aqueous conidia suspension of wheat nivale (var. nivale).
The plants were then placed in a greenhouse under a clear plastic ceiling at a temperature of about 15 ℃ and a relative atmospheric humidity of about 100%.
Evaluation was performed 4 days after inoculation. 0% means that the efficacy is comparable to the control, whereas 100% means that no infection is observed.
In this test, the substances according to the invention described in examples (1) and (2) show an efficiency of 90% or more at an application rate of 250 g/ha.
Example D
Downy mildew (Plasmopara) test (grape)/protective
Solvent: 47 parts by weight of acetone
Emulsifier: 3 parts by weight of alkylaryl polyglycol ether
To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
When testing for protective activity, young plants are sprayed with the preparation of active compound at the stated dose. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola. The plants were then placed in a culture chamber at about 20 ℃ and 100% relative atmospheric humidity for 1 day. Followed by 5 days in a greenhouse at about 21 ℃ and about 90% relative atmospheric humidity. The plants were then moistened and placed in a culture chamber for 1 day.
Evaluation was performed 6 days after inoculation. 0% means that the efficacy is comparable to the control, whereas 100% means that no infection is observed.
In this test, the substances according to the invention of examples (1), (2), (3), (4), (5), (6), (7), (9), (10), (11), (13), (14), (15), (17), (19), (20), (34), (48), (50), (51), (53) and (59) have an efficiency of 90% or more at an application rate of 100 g/ha.
Example E
Sphaerotheca test (cucumber)/protective
Solvent: 47 parts by weight of acetone
Emulsifier: 3 parts by weight of alkylaryl polyglycol ether
To prepare a suitable formulation of the active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating had dried, an aqueous spore suspension of the fungus Xanthium sibiricum (Sphaerotheca fuliginea) was inoculated onto the plants. The plants were then placed in a greenhouse at about 23 ℃ and a relative atmospheric humidity of about 70%.
Evaluation was performed 10 days after inoculation. 0% means an efficacy corresponding to that of the control, whereas an efficacy of 100% means that no infection is found.
In this test, the substances according to the invention of examples (1), (2), (3) and (4) have an efficacy of 90% or more at an application rate of 100 g/ha.
Example F
Venturia (Venturia) test (apple)/protective
Solvent: 47 parts by weight of acetone
Emulsifier: 3 parts by weight of alkylaryl polyglycol ether
To prepare a suitable formulation of the active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the sprayed layer had dried on, the plants were inoculated with an aqueous conidia suspension of pathogenic microorganisms of the species Venturian inaequalis, the scab apple scab. The inoculum was placed in a greenhouse at about 20 ℃ and 100% relative atmospheric humidity for 1 day.
The plants were then placed in a greenhouse at about 21 ℃ and a relative atmospheric humidity of about 90%.
Evaluation was performed 12 days after inoculation. 0% means an efficacy corresponding to that of the control, whereas an efficacy of 100% means that no infection is found.
In this test, the substances according to the invention of examples (2), (3), (4), (5), (7), (10), (11), (12), (13), (17), (20), (21), (22), (23), (24), (31), (36), (40), (48) and (59) show an efficacy of 90% or more at an application rate of 10 g/ha.
Example G
Rice blast (Pyricularia) test (rice)/protective
Solvent: 2.5 parts by weight of acetone
Emulsifier: 0.06 parts by weight of alkylaryl polyglycol ether
To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
In testing for protective activity, rice seedlings are sprayed with the active compound preparation in the stated dosage. After the spray coating has dried, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae (Pyricularia oryzae). The plants were then placed in a greenhouse at 100% relative atmospheric humidity and 25 ℃.
Evaluation was performed 4 days after inoculation. 0% means that the efficacy is comparable to the control, whereas 100% means that no infection is observed.
In this test, the substances according to the invention of examples (1), (3), (4) and (7) have an efficiency of 90% or more at an application rate of 750 g/ha.
Claims (11)
1. A compound of the formula (I),
wherein
Z represents cycloalkyl, aryl, aralkyl, heterocyclyl or heterocycloalkyl, which are optionally substituted,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
x represents a halogen atom or a halogen atom,
L1、L2、L3and L4Are identical or different and each independently represents hydrogen, halogen, cyano, nitro, or representsAlkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each optionally substituted by halogen.
2. A compound of formula (I) according to claim 1, wherein
Z represents cycloalkyl or cycloalkylalkyl having in each case 3 to 7 carbon atoms in the cycloalkyl moiety and 1 to 4 carbon atoms in the alkyl moiety and in each case optionally mono-to penta-substituted by halogen or alkyl,
represents heterocyclyl or heterocyclylalkyl having from 1 to 4 carbon atoms in the alkyl part and in each case optionally substituted by halogen, dialkylamino or alkyl having from 1 to 4 carbon atoms and each having from 3 to 7 ring members, or
Represents aryl or arylalkyl each having from 6 to 10 carbon atoms in the aryl moiety and from 1 to 4 carbon atoms in the alkyl moiety and each being optionally mono-to tetrasubstituted by identical or different substituents, the possible substituents preferably being selected from:
halogen, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl,
alkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl, each having 1 to 8 carbon atoms and each being straight-chain or branched,
alkenyl or alkenyloxy having in each case 2to 6 carbon atoms and in each case straight-chain or branched,
haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms and in each case straight-chain or branched,
halogenoalkenyl or halogenoalkenyloxy having in each case 2to 6 carbon atoms and 1 to 11 identical or different halogen atoms and in each case straight-chain or branched,
alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, alkenylcarbonyl or alkynylcarbonyl having from 1 to 6 carbon atoms in the hydrocarbon-based moiety concerned and each being straight-chain or branched,
cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms,
alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, each of which is doubly linked and each is optionally mono-to tetrasubstituted identically or differently, by substituents selected from the group consisting of fluorine, chlorine, oxo, methyl, trifluoromethyl and ethyl, or
A group of the formula:
wherein,
A1represents hydrogen or alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, and
A2represents hydroxyl, amino, methylamino, methyl, phenyl, benzyl, alkoxy, alkylamino, dialkylamino, having 1 to 4 carbon atoms in the alkyl chain in question,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
x represents fluorine, chlorine or bromine, and
L1、L2、L3and L4Are identical or different and each independently represent hydrogen, halogen, cyano, nitro, or represent alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each having 1 to 6 carbon atoms and each being optionally substituted by 1 to 5 halogen atoms.
3. A compound of formula (I) according to claim 1, wherein
Z represents cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally mono-to pentasubstituted by fluorine, chlorine, methyl or ethyl,
represents thienyl, pyridyl, furyl, thienylmethyl, pyridylmethyl or furylmethyl, each of which is optionally substituted by methyl, ethyl, dimethylamino, fluorine, chlorine or bromine, or
Represents phenyl or benzyl, each of which is optionally mono-to tetrasubstituted by identical or different substituents, possible substituents being selected from the group consisting of:
fluorine, chlorine, bromine, cyano, nitro, amino, formyl, carbamoyl, thiocarbamoyl,
methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxymethyl,
methoxy, ethoxy, n-or i-propoxy,
methylthio, ethylthio, n-or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl,
a methyl-aminomethyl group, a dimethyl-aminomethyl group,
vinyl, allyl, 2-methallyl, propen-1-yl, butenyl, propargyl, vinyloxy, allyloxy, 2-methallyloxy, propen-1-yloxy, butenyloxy, propargyloxy,
a trifluoromethyl group and a trifluoroethyl group,
difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, pentafluoroethoxy, 2-chloro-1, 1, 2-trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl,
methylamino, ethylamino, n-or i-propylamino, dimethylamino or diethylamino,
acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acryloyl or propioyl,
a cyclopentyl group and a cyclohexyl group,
propylene glycol, ethyleneoxy, methylenedioxy, ethylenedioxy, each of which is doubly linked and each of which is optionally mono-to tetrasubstituted identically or differently by substituents from the group consisting of fluorine, chlorine, oxo, methyl and trifluoromethyl, or
A group of the formula:
wherein,
A1represents hydrogen or methyl, and
A2represents hydroxy, methoxy, ethoxyAmino, methylamino, methyl, phenyl or benzyl,
q represents oxygen or sulphur, and Q represents oxygen or sulphur,
x represents fluorine or chlorine, in particular fluorine, and
L1、L2、L3and L4Are identical or different and each independently represents hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-or i-propyl, n-, i-, s-or t-butyl, methoxy, ethoxy, n-or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl.
4. Pesticides, characterized in that they contain at least one compound of the formula (I) according to claim 1.
5. A method for controlling pests, characterized in that a compound of formula (I) according to claim 1 is allowed to act on the pests and/or their habitat.
6. Use of a compound of formula (I) or a composition according to any one of claims 1 to 4 for controlling pests.
7. A process for the preparation of a pesticide, characterized in that a compound of formula (I) according to any one of claims 1 to 3 is mixed with an extender and/or a surfactant.
8. A process for the preparation of a compound of formula (I) characterized in that:
a) if appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, reacting 3- (2-hydroxyphenyl) -3-methoxyiminomethyloxadiazines of the general formula (II) with substituted halogenopyrimidines of the general formula (III),
wherein,
L1、L2、L3and L4Each as defined in claim 1, wherein,
wherein,
z, Q and X are each as defined in claim 1,
Y1represents halogen, or
b) If appropriate in the presence of a diluent, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst, with a ring compound of the formula (V),
wherein,
X、L1、L2、L3and L4Each as defined in claim 1, wherein,
Y2represents a halogen atom or a halogen atom,
Z-Q-H (V) wherein,
z and Q are each as defined in claim 1.
9. A compound of the formula (II),
wherein
L1、L2、L3And L4Each as defined in claim 1.
10. A compound of the formula (VI),wherein
L1、L2、L3And L4Each as defined in claim 1, and
Y3represents halogen, alkylsulfonyl or arylsulfonyl.
11. A compound of the formula (IV),
wherein
X、L1、L2、L3And L4Each as defined in claim 1, and
Y2represents halogen.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19735196 | 1997-08-14 | ||
| DE19735196.4 | 1997-08-14 | ||
| DE19737723.8 | 1997-08-29 | ||
| DE19737723A DE19737723A1 (en) | 1997-08-14 | 1997-08-29 | New methoximino:methyl-di:hydro-1,2,4-oxadiazine derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1267301A true CN1267301A (en) | 2000-09-20 |
Family
ID=26039124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98808157A Pending CN1267301A (en) | 1997-08-14 | 1998-08-01 | Methoximinomethyloxadiazines used as pesticides |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6251899B1 (en) |
| EP (1) | EP1003742A1 (en) |
| JP (1) | JP2001515076A (en) |
| CN (1) | CN1267301A (en) |
| AU (1) | AU9256898A (en) |
| BR (1) | BR9811939A (en) |
| ID (1) | ID24435A (en) |
| IL (1) | IL134002A0 (en) |
| WO (1) | WO1999009026A1 (en) |
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| DE19819828A1 (en) * | 1998-05-04 | 1999-11-11 | Bayer Ag | Methoximinomethyloxathiazine |
| DE19955130A1 (en) | 1999-11-17 | 2001-05-23 | Bayer Ag | Hydroxamic acid derivatives |
| DE10014607A1 (en) | 2000-03-24 | 2001-09-27 | Bayer Ag | Production of asymmetric 4,6-bis(aryloxy)-pyrimidine derivatives comprises two stage reaction of 4,6-dichloro-pyrimidine with phenols using 1,4-diazabicyclo(2.2.2)octane in second reaction stage |
| ES2295816T3 (en) | 2003-01-14 | 2008-04-16 | Arena Pharmaceuticals, Inc. | ARILO AND HETEROARILO 1,2,3-TRISUSTITUTED DERIVATIVES AS METABOLISM MODULATORS, AND PROFILAXIS AND TREATMENT OF DISORDERS RELATED TO THE SAME, SUCH AS DIABETES AND HYPERGLUCEMIA. |
| AR045047A1 (en) | 2003-07-11 | 2005-10-12 | Arena Pharm Inc | ARILO AND HETEROARILO DERIVATIVES TRISUSTITUIDOS AS MODULATORS OF METABOLISM AND PROFILAXIS AND TREATMENT OF DISORDERS RELATED TO THEMSELVES |
| EP2619198A1 (en) | 2010-09-22 | 2013-07-31 | Arena Pharmaceuticals, Inc. | Modulators of the gpr119 receptor and the treatment of disorders related thereto |
| US9193698B2 (en) | 2013-07-08 | 2015-11-24 | Advinus Therapeutics, Ltd. | Process for preparing fluoxastrobin |
| PL3242666T3 (en) | 2015-01-06 | 2025-02-17 | Arena Pharmaceuticals, Inc. | Compound for use in treating conditions related to the s1p1 receptor |
| JP6838744B2 (en) | 2015-06-22 | 2021-03-03 | アリーナ ファーマシューティカルズ， インコーポレイテッド | (R) -2- (7- (4-cyclopentyl-3- (trifluoromethyl) benzyloxy) -1,2,3,4-tetrahydrocyclopenta [b] indole-for use in S1P1 receptor-related disorders Crystalline L-arginine salt of 3-yl) acetic acid (Compound 1) |
| KR102859841B1 (en) | 2018-06-06 | 2025-09-12 | 아레나 파마슈티칼스, 인크. | Treatment of conditions associated with the S1P1 receptor |
| AR117461A1 (en) * | 2018-12-20 | 2021-08-04 | Bayer Ag | HETEROCYCLYL PYRIDAZINE COMPOUNDS AS FUNGICIDES |
| KR20230024343A (en) * | 2020-06-10 | 2023-02-20 | 바이엘 악티엔게젤샤프트 | Azabicyclyl-substituted heterocycles as fungicides |
| EP4167740A1 (en) * | 2020-06-18 | 2023-04-26 | Bayer Aktiengesellschaft | Active compound combinations |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1273921A (en) * | 1982-09-28 | 1990-09-11 | Walter G. Brouwer | 3-aryl-5, 6-dihydro-1, 4, 2-oxathiazines and their oxides |
| GB9307247D0 (en) * | 1993-04-07 | 1993-06-02 | Zeneca Ltd | Fungicidal compounds |
| ZW8594A1 (en) * | 1993-08-11 | 1994-10-12 | Bayer Ag | Substituted azadioxacycbalkenes |
| DE4340181A1 (en) | 1993-11-25 | 1995-06-01 | Bayer Ag | 3-methoxy-2-phenyl-acrylic acid methyl ester |
| US6214825B1 (en) * | 1995-02-13 | 2001-04-10 | Bayer Aktiengesellschaft | Aza-heterocycloakenes, pesticidal compositions containing them, pesticidal methods of using them, and processes for preparing them |
| TW492962B (en) * | 1996-05-30 | 2002-07-01 | Bayer Ag | Process for preparing 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines |
| DE19706396A1 (en) * | 1996-12-09 | 1998-06-10 | Bayer Ag | Process for the preparation of 3- (l-hydroxiphenyl-l-alkoximinomethyl) dioxazines |
-
1998
- 1998-08-01 JP JP2000509707A patent/JP2001515076A/en not_active Withdrawn
- 1998-08-01 IL IL13400298A patent/IL134002A0/en unknown
- 1998-08-01 US US09/485,379 patent/US6251899B1/en not_active Expired - Fee Related
- 1998-08-01 EP EP98945137A patent/EP1003742A1/en not_active Withdrawn
- 1998-08-01 CN CN98808157A patent/CN1267301A/en active Pending
- 1998-08-01 ID IDW20000265A patent/ID24435A/en unknown
- 1998-08-01 AU AU92568/98A patent/AU9256898A/en not_active Abandoned
- 1998-08-01 WO PCT/EP1998/004821 patent/WO1999009026A1/en not_active Ceased
- 1998-08-01 BR BR9811939-7A patent/BR9811939A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001515076A (en) | 2001-09-18 |
| BR9811939A (en) | 2000-09-05 |
| IL134002A0 (en) | 2001-04-30 |
| WO1999009026A1 (en) | 1999-02-25 |
| EP1003742A1 (en) | 2000-05-31 |
| ID24435A (en) | 2000-07-20 |
| AU9256898A (en) | 1999-03-08 |
| US6251899B1 (en) | 2001-06-26 |
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